Process of preparing nitrogenous cellulose derivatives



atented fective for the animalizing of cellulose- PRocEss or PREPARING mTRoGENoUs CELLULOSE DERIVATIVES Louis H. Bock, Glenside, and Alva L. Honk, Philadelphia, Pa., assignors to litiihm & Haas Company, Philadelphia, Pa.

No Drawing. Application October 21, 1939,

Serial No. 800,654

6 Claims.

. part to the cellulosic materials improved properties. In particular, it deals with imparting to cellulose permanently improved properties as shown by the handle, feel, appearance, and resistance to water of the treated material, decreased shrinkage on wetting and by the capacity of the treated cellulosic material to take up and hold dyestuffs which ordinarily are of value only with wool and silk.

Although many processes have been suggested for animalizing lacked the simplicity and economy essential for practical application or have brought about such changes in the fibers that they were no longer suitable for the purposes originally intended and that the fundamental advantages of cellulose fibers have bene lost. We have found, furthermore, that many types of nitrogen linkage which have been added to cellulose are not truly efis the coating of cellulose with nitrogenous resins truly efiective in accomplishing our objects.

It is the object of this invention to form nitrog enous derivatives of cellulose which improve the usual properties thereof. It is an object to impart tocellulose fibers a desirable finish as to.

- that by the proper choice of substituents in the triazine group a wide range of efiects'may be produced. Thus the cellulose may be rendered moderately soft or given a full, pleasing hand. It long chain derivatives are selected, water-proof or water-resistant effects are obtained. Cellulose treated with aminotriazines becomes markedly receptive to dyes ordinarily used only with wool and silk. We have found that the type of nitrogen linkages imparted in this process is unusually ef-- Elective in animalizlng cellulose. The treatment may be given only to the surface of, the cellulosic material, particularly when dilute solutions are cellulose fibers,- they have 15 Nor applied, or by thorough impregnation with the treating solution the cellulose may become in relatively large part converted to an organic substitution derivative of cellulose containing a methylene amino-1,3,5-triazine group.

As cellulosic materials there may be used cotton, linen, jute, hemp, or other natural fibers of cellulose, or the cellulosic materials prepared from cotton, linters, wood cellulose, or the like by solution and regeneration and which are particularly improved by the treatment herein described. Mercerized cotton and linen, hydrated cellulose,

cellulose ethers, and cellulose esters, in short any type of water-insoluble cellulosic material possessing hydroxyl groups, may be treated by our process. The cellulose may be in the form of fabrics,-fibers, yarns, battingss'neets, or strips and may be fibrous or'non-fibrous.

The aminomethylene amino-1,3,5-triazines, used for treating cellulose, are prepared by reacting an amino-1,3,5-triazine with formaldehyde and a non-aromatic monoamine possessing a hydrogen atom attached to the nitrogen. The preparation of such condensates is described in detail in our copending application Serial No. 300,548 filed October 21, 1939, which on August 6, 1940, issued as United States Patent No. 2,210,831. There may be reacted at least one mol each of formaldehyde and the amine for each moi of an amino-1,3,5-triazine, and as many as three to six mols of each may be reacted with a mol of a triazine possessing a like number of positions available for substitution. Aminomethylene derivatives may be obtained from ammelide, ammeline, melamine and any of their derivatives containing an amino group, representative eE- amples of which are the diacyl ammelines, such as distearyl ammeline, the preparation of which is described in our copending application Serial No. 300,549 filed October 21, 1939, which on February 1'7, 1942, issued as U. S. Patent No. 2,273,687, or the 2-alkyl, 4-amino-6 hydroxyl,3,5-triazines, and similar compounds in which the triazine group carries an aliphatic, aromatic, aralkyl, alicyclic, or heterocyclic substituent, or a halogen, cyano group, or other group such as i cyano-Z-amino-4,6-dimethyl-1,3,5-triazine or 2- chloro-4,5-diamino-1,3,5-triazine, or from tautomers of such compounds.

The preferred aminotriazine derivatives are those synthesized from one molar proportion of an amino-1,3,5-triazine and at least one mol each of formaldehyde any of its various forms and an amine having at-leastone hydrogen atom attached tothe' amine nitrogen atom and possessing no substituent group of over eight carbon atoms, since this amino groupis split out .in the reaction of anaminomethylene amino-1,3,5-triazine with cellulose. The most satisfactory derivatives are those prepared from non-aromatic,

strongly basic, secondary amines.

Typical amines which may be used include monomethylamine, dimethylamine, monobutyletc. which formsalts with the amino groups.

The solutions or dispersions are stable and may be applied cold or hot, as desired. The presence of acids or salts of a strong acid and weak base seems to aid in the reaction with cellulose. A1- kaline materials, such as soda ash; borax, sodium acetate (salts of a strong base and a weak acid) are also effective as catalysts.

Cellulosic material is impregnated withthe so-.

lution or dispersion by immersion, dipping, or spraying, preferably followed by passage through squeeze rolls. Cellulosic fabrics may also be printed with a solution or paste, thus producing local effects. The-impregnated material is dried at room temperature or above and heated to 'a temperature preferably between 90 C. and 130 C. In this temperature range the reaction between cellulose andthe aminomethylene aminotriazine takes place in a short time with the triazine nucleus becoming chemically combined with the cellulose. Somewhat lower temperatures and higher temperatures are also effective. Drying and heating may constitute one continuous operation. After the step involving heating, the treated material may be washed to remove unreacted material. or decomposition products from the reacted aminomethylene amino-1,3,5-triazine.

. The animalizing of the cellulose may be combined with a sizing operation resulting in simultaneous fixation ofthe size as disclosed. in

our copending application Serial No. 300,655 flied Oct. 21, 1939, which on NOV. 10, 1942, issued .88 U. 8. .Patent NO. 2,301,509 and "animalizing" of the cellulose. In the preferred procedure the operation of dyeing follows the modifying of the cellulose.- The treated cellulose is receptive to acid andbasic dyes and many other dyestufls which are normally used only on wool or silk.-

The aminomethylene amino-1,3,5-triazines are also useful in conjunction with resin-finishing of fabrics, serving as softening agents when the triazine group carries. a hydrocarbon substituent of twelve or more carbon atoms.

Typical treatments of various cellulosic materials are shown-in the following exam les- Example 1.A bleached cotton fa ric was coated with a composition containing 12.5% of tris(dimethylaminomethyl) melamine, 3.5% of water-soluble hydroxyethyl cellulose, 1% acetic acid and 83% ofwater. It was dried, heated onehalf hour at 130' C., and washed. It was then dyed one-half hour in a boiling. .5% solution of Iontacyl Carmine 68 containing 1% of acetic acid and took on a medium dark red shade,

which was fastto washing.

Example 2.- -Cotton fabric was dipped through a ample 1, a medium shade of color was obtained which was fast to washing.

Example 4.A viscose rayon fabric was dipped through a paste comprising 12.5 parts of the 4 bis- (dimethylaminomethyl) derivative oi melamine, 4% of potato starch, 5% of acetic acid, and '18.5% of water. It was then dried, heated at 130 C. for twenty minutes, and washed. The dyeing operation, performed as in Example 1,

gave a deep color. which was retained on washing.

Example -5.Cellulose acetate fabric was dipped through an aqueous solution containing 25% of the tris-(dimethylaminomethyl) derivative of dibutyl ammeline. It was then dried, heated at 130 .C. for twenty minutes, and dyed at the boil with Pontacyl Carmine 6B. The cellulose acetate was dyed to a medium red shade which was fastto washing.

Example 6.-Cotton fabric was dipped through a 12% solution of dimethylaminomethyl ammelide acidified with acetic acid and was squeezed. It was dried, baked one-half hour at 130 C., and washed. Upon immersion at 95 C. for twenty minutes in s. 0.5% fuchsin solution, it acquired a deep wine-red color, resistant to washing.

Example 7.Cotton fabric was dipped through a paste comprising four parts of a 7%.; aqueous solution of hydroxyethyl cellulose and 1 part of bis-(dimethylaminomethyl) melamine hydrochloride. After removing theexcess with a. squeeze roll, the fabric was heated one-half hour at 130C. and washed. Treatment of the stillened fabric with fuchsin as in Example 6 gave a wine-red color, which was permanent.

Example 8.Linen fabric was treated according to Example 6. With the same basic'dye, it gave a medium wine-red shade, resistant to washing.

Example 9. Cotton sheeting was run through an aqueous solution containing 5% of bis-(di- The results were similar, a high degree of resistance to wetting and of softness being obtained. Example 11.'-Cotton sheeting was coated with a paste contatining 5% of dimethylaminomethylene distearyl ammeline and 0.25% of sodium carbonate. It was baked one-half hour at 140 C. A water-repellent finish was obtained. The

hand was full, soft, with a dry, wax-like-feel.

' methyl distearyl ammeline.

'90 and about 140. C.

Example 12'.-A rayon. pile fabric was impregnated with a 2% solution of bis dimethylamino- It was baked onehalf hour at 125 C. A soft hand was obtained and resistance to wetting.

Example 13.-A piece. of 80 "x 80, 4-yard, 36-

inch cotton sheeting was fastened in a rigid frame and treated under tension witha 15% aqueous solution of tri's(dimethylaminomethyl) melaminehydrochloride. It was placed in an oven without drying and held at 130 C. for

- twenty minutes. 7 After a soap wash at-140 F.

for one-half hour, it had shrunk 2.5% in the warp-wise dimension. A control shrank 5.0%.

We claim: 1. A method for preparing nitrogenous cellulose derivatives on water-insoluble cellulosic materials in the form of fabrics, yarns, fibers,

battings, sheets, and strips' which comprises treating the cellulosic material with a solution of azine and at least molecular proportions of formaldehyde and dimethylamine, and heating the treated material to a temperature between about '20 a condensation product of an amino-1,3,5-trithe treated material to a temperature between about 90 and about 140 C.

lose derivatives on water-insoluble cellulosic materials in the form of fabrics, yarns, fibers,

b attings, sheets, and strips which comprises treating the cellulosic material with a solution of a condensate of melamine and at least molecular proportions each of formaldehyde and dimethylamine, and subsequently heating the treated material to a temperature between about 90 and about 140 C.

, 4. A method for preparing nitrogenous-derivatives on fabrics, yarns, fibers, battings, sheets, and strips composed of water-insoluble regenerated cellulose which comprises treating said regenerated cellulose with a solution of a condensation product of an amino-1,3,5-triazin with at least molecular proportions each of formaldehyde and dimethylamine, and subsequently heating the thus treated cellulose to a temperaturebetween about 90 and; about 140 C.

5, Cellulosic textile fabric carrying a complex" reaction product formed by heating to a temperature between about 90 C. and about 140 C. cellulose and a condensation product of melamine with at least molecular proportions each .of formaldehyde and dimethylamine.

6. A cellulosic textile fabric carrying a complex reaction product formed by heating to a temperature between about 90 C. and about 140 C.- cellulose'and acondensation product of distearyl I ammeline with at least molecular proportions each of formaldehyde and dimeth ylamine.

Louis H. BOCK. ALVA L. from 3. A method for preparing nitrogenous cellu- 

